Extended-chain crystals (ECCs) of poly(butylene succinate) (PBS), featuring highly ordered molecular chains and exceptional thermal stability with a melting point 25 °C higher than conventional folded-chain crystals, demonstrate remarkable potential as nucleating agents for PBS crystallization. The incorporation of 5 wt% ECCs leads to a 12 °C increase in crystallization temperature and reduces crystallization half-time by 88% at 98 °C. Most significantly, self-nucleation studies reveal an unprecedented expansion of Domain II temperature window (∆T = 30 °C), exhibiting enhanced melt memory effects and a broadened processing window. Rheological investigations uncover the formation of unique intermolecular interactions in the melt, evidenced by non-terminal viscoelastic behavior and reduced loss tangent at elevated temperatures, with complementary evidence from higher ECC loadings confirming these findings. This local ordered structure exhibits remarkable thermal stability, persisting even above the melting point through specific intermolecular interactions, leading to the melt memory effect. These findings establish a new paradigm for nucleation control in biodegradable polyesters and provide molecular design strategies for high-performance sustainable materials.

Crystalline/crystalline blends of polymer have shown advantages in the preparation of new polymeric materials. However, the regulation of co-crystallization in a blend is still full of challenges due to the preferential self-crystallization driven by thermodynamics. Here, an inclusion complex approach is proposed to facilitate the co-crystallization between crystalline polymers, because the crystallization process displays a prominent kinetics advantage when polymer chains are released from the inclusion complex. Poly(butylene succinate) (PBS), poly(butylene adipate) (PBA) and urea are chosen to form co-inclusion complexes, where PBS and PBA chains play as isolated guest molecules and urea molecules construct the host channel framework. The coalesced PBS/PBA blends are obtained by fast removing the urea framework and systematically investigated by differential scanning calorimetry, X-ray diffraction, proton nuclear magnetic resonance and Fourier transformation infrared spectrometry. It is demonstrated that PBA chains are co-crystallized into PBS extended-chain crystals in the coalesced blends, while such a phenomenon has not been detected in simply co-solution-blended samples. Though PBA chains could not be totally accommodated in the PBS extended-chain crystals, their co-crystallized content increases with the initial feeding ratio of PBA. Consequently, the melting point of the PBS extended-chain crystal gradually declines from 134.3 °C to 124.2 °C with an increasing PBA content. The PBA chains playing as defects mainly induce lattice expansion along the a-axis. In addition, when the co-crystals are soaked in tetrahydrofuran, some of the PBA chains are extracted out, leading to damage to the correlative PBS extended-chain crystals. This study shows that co-inclusion complexation with small molecules could be an effective way to promote co-crystallization behavior in polymer blends.